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CN110734579A - Plasticizer, resin composition, and method for producing same - Google Patents

Plasticizer, resin composition, and method for producing same Download PDF

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Publication number
CN110734579A
CN110734579A CN201911042139.1A CN201911042139A CN110734579A CN 110734579 A CN110734579 A CN 110734579A CN 201911042139 A CN201911042139 A CN 201911042139A CN 110734579 A CN110734579 A CN 110734579A
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Prior art keywords
plasticizer
terephthalate
isophthalate
alcohol
acid
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Inventor
金显圭
郑茶苑
李美然
高东铉
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LG Corp
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LG Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C07C69/82—Terephthalic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/18—Plasticising macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to plasticizers, resin compositions and methods for preparing the same, which can improve the poor physical properties due to the structural limitations of the plasticizer, although the plasticizer has environmental protection characteristics, to provide plasticizers which can improve the light resistance required for the formulation of a composite or the physical properties such as viscosity, bleeding (gelation) phenomenon and gelation characteristics required for the formulation of a sheet material when used as a plasticizer for a resin composition, and a resin composition containing the plasticizer.

Description

Plasticizer, resin composition, and method for producing same
Technical Field
The present invention relates to plasticizers, resin compositions, and methods for producing the same, and more particularly, to a plasticizer, a resin composition, and methods for producing the same, which can improve undesirable physical properties that occur due to structural limitations, despite their environmentally friendly characteristics.
Background
the plasticizer reacts with phthalic acid and polycarboxylic acid such as adipic acid to form corresponding ester, and further, considering that the phthalate plasticizer harmful to the human body is restricted by regulations at home and abroad, various environmentally friendly plasticizers capable of replacing phthalate plasticizers such as terephthalate, adipic acid, and other high molecular weight plasticizers have been continuously studied.
In addition, , in order to produce floor materials, wall papers, products in the sheet industry, etc., which require physical properties with light resistance, it is necessary to use an appropriate plasticizer in consideration of discoloration factors, and in the case of PVC compounds for wall papers or sheets, it is necessary to add and mix a plasticizer, a filler, a stabilizer, a viscosity reducer, a dispersant, an antifoaming agent, a foaming agent, etc., to PVC resins in accordance with characteristics such as tensile strength, elongation, light resistance, bleeding phenomenon, gelation, etc., required by the respective specifications.
As exemplified in , when dioctyl phthalate, which is inexpensive among environmentally friendly plasticizers that can be used in PVC, is used, the viscosity is high and the absorption rate of the plasticizer is relatively slow, so that not only a bleeding phenomenon will be observed on the back surface of the raw material but also the gelation property is not excellent.
Therefore, research is continuously conducted to develop a product more excellent than the dioctyl phthalate, or a novel composition product containing the dioctyl phthalate, so that the product can be optimally applied as a plasticizer for vinyl chloride-based resins.
Prior art documents
Patent document
Patent document 1: korean patent laid-open No. 2006-0087889 (2006.08.03)
Disclosure of Invention
Technical problem
Therefore, the present inventors have completed the present invention by confirming an environmentally friendly plasticizer capable of improving the poor physical properties due to structural limitations although having environmental characteristics, while continuously studying the plasticizer.
That is, an object of the present invention is to provide kinds of plasticizers which can improve physical properties such as light resistance required for a composite formulation or viscosity, bleeding phenomenon, gelation properties required for a sheet formulation when used as a plasticizer for a resin composition, a method for producing the same, and a resin composition containing the same.
Means for solving the problems
According to the present invention, there are provided kinds of plasticizers characterized by containing isophthalate and terephthalate.
Further, according to the present invention, there is provided a method for preparing plasticizers, which comprises:
a step of simultaneously charging isophthalic acid and terephthalic acid in the presence of an alcohol, thereby obtaining a mixture;
a step of adding a catalyst to the mixture and reacting the mixture under a nitrogen atmosphere;
a step of removing the unreacted alcohol and neutralizing the unreacted acid; and
a step of obtaining a plasticizer by dehydrating and filtering by distillation under reduced pressure.
Further, according to the present invention, there is provided a method for preparing plasticizers, which comprises:
preparing an ester mixture containing terephthalate and isophthalate; and
a step of mixing the terephthalate and isophthalate esters, including 1 to 99 wt% of the isophthalate ester, based on the total weight of the mixture, to thereby obtain the plasticizer according to claim 1.
Further, the present invention provides resin compositions, wherein the plasticizer is contained in an amount of 5 to 150 parts by weight per 100 parts by weight of a resin selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer.
Advantageous effects
According to the present invention, it is possible to provide a plasticizer which can improve physical properties such as light resistance required for a composite formulation, viscosity, bleeding (gelation) phenomenon, gelation property required for a sheet formulation, and the like when used as a plasticizer for a resin composition by improving poor physical properties occurring due to structural restrictions although the plasticizer has environmental characteristics, and a resin composition containing the plasticizer.
Detailed Description
The present invention will be described in detail below.
First, the present invention has a technical feature of providing kinds of plasticizers capable of improving poor physical properties due to structural limitations, although having environmental protection characteristics.
According to an embodiment of the present invention, there are provided plasticizers characterized by containing isophthalate and terephthalate esters.
The plasticizer according to the present invention is used as environment-friendly plasticizer, and the term "environment-friendly plasticizer" means ether-free (ether-free) ester-free plasticizer or ether-free phthalate-type plasticizer, unless otherwise specified.
The term "ether-free" means that the ether component contained in the plasticizer is 1,000ppm or less, 100ppm or less, or 10ppm or less.
In the plasticizer according to example of the present invention, the mixing ratio of isophthalate to terephthalate may be 1:99 to 99:1 by weight.
In the plasticizer according to example of the present invention, the mixing ratio of the isophthalate and the terephthalate may be 20:80 to 99:1 by weight, 50:50 to 99:1 by weight, or 50:50 to 90:10 by weight.
In addition, in the plasticizer according to example of the present invention, the mixing ratio of isophthalate to terephthalate may be 60:40 to 90:10 by weight.
In embodiments according to the invention, plasticizers can be provided that include 1 to 99 wt%, 20 to 99 wt%, or 50 to 99 wt% of isophthalate and 50 to 90 wt%, or 60 to 90 wt% of terephthalate, based on the total weight of the plasticizers.
Specifically, in the plasticizer according to the example of the present invention, the content of isophthalate may be equal to or greater than the content of terephthalate.
In the plasticizer according to example of the present invention, when the isophthalate having a content greater than or equal to the terephthalate content is used, the hardness and elongation are significantly improved in the production of a composite or sheet, etc., thereby being capable of contributing to the production efficiency and the working efficiency of the product and having a significant effect of improving the rate-increasing efficiency.
For example , the isophthalate can have terminal groups independently selected from alkyl groups having 1-12, 3-11, 4-10, 8-9, or 8 carbon atoms.
According to the plasticizer of of the present invention, the isophthalate has a terminal group selected from alkyl groups having 8 to 10 carbon atoms, and therefore, the migration resistance and heating loss can be significantly improved as compared with the case where the ester in the plasticizer has a terminal group selected from alkyl groups having 7 or less carbon atoms.
Therefore, the plasticizer according to of the present invention preferably contains an isophthalic acid ester containing an ester having a terminal group selected from alkyl groups having 8 to 10 carbon atoms, in order to improve migration resistance and heating loss.
In the plasticizer according to , the isophthalate may be dialkyl isophthalate, and the alkyl group may be an alkyl group having 1 to 12 carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon atoms, 8 to 9 carbon atoms, or 8 carbon atoms.
As another example, the isophthalate can have a structure represented by formula 1 below.
[ chemical formula 1]
Figure BDA0002251534770000051
In addition, the plasticizer according to of the present invention may contain 1 to 99 wt%, 1 to 80 wt%, 1 to 50 wt%, 10 to 50 wt%, or 10 to 40 wt% of terephthalate, based on the total weight of the plasticizer.
The terephthalate may have a terminal group independently selected from the group consisting of C1-12, C3-11, C4-10, C8-9, and C8 alkyl groups.
As a specific example, the terephthalate may contain an alkyl group having the same number of carbon atoms as the terminal group of the isophthalate as described above.
According to of the present invention, since the terephthalate has a terminal group selected from an alkyl group having 8 to 10 carbon atoms, the migration loss and heating loss can be significantly improved as compared with the case where the ester in the plasticizer has a terminal group selected from an alkyl group having 7 or less carbon atoms.
Therefore, the plasticizer according to of the present invention preferably contains a terephthalate ester containing an ester having a terminal group selected from alkyl groups having 8 to 10 carbon atoms, in order to improve migration loss and heating loss.
In the plasticizer according to , the terephthalate may be a dialkyl terephthalate, and the alkyl group may be an alkyl group having 1 to 12 carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon atoms, 8 to 9 carbon atoms, or 8 carbon atoms.
As another example, the terephthalate can have a structure represented by formula 2 below.
[ chemical formula 2]
The plasticizer can be prepared by an pot (one pot) preparation method or a blending method preparation method, and is exemplified by , and a pot preparation method is as follows.
That is, isophthalic acid is added in the presence of an alcohol (hereinafter referred to as step).
A catalyst was added to the mixture and allowed to react under a nitrogen atmosphere.
Thereafter, the unreacted alcohol is removed and the unreacted acid is neutralized.
Next, the plasticizer can be prepared by dehydration and filtration by distillation under reduced pressure.
Specifically, the isophthalic acid and the terephthalic acid may be added in a weight ratio of 20:80 to 99:1, 50:50 to 99:1, or 50:50 to 90: 10.
Further, as another example, isophthalic acid and terephthalic acid may be added in a weight ratio of 60:40 to 90: 10.
Further, with the example, the blending process is prepared as follows.
Terephthalate and isophthalate esters were prepared.
The plasticizer may be prepared by a blending method, and the terephthalate and the isophthalate are blended so as to contain 1 to 99 wt%, 20 to 99 wt%, or 50 to 99 wt% of the isophthalate and 50 to 90 wt%, or 60 to 90 wt% of the terephthalate, based on the total weight of the plasticizer.
In the blend method production method, the terephthalate may be prepared by a step of adding terephthalic acid to an alcohol, then adding a catalyst, and reacting the mixture in a nitrogen atmosphere; a step of removing the unreacted alcohol and neutralizing the unreacted acid; and a step of dehydrating and filtering by vacuum distillation.
In the blend method, the isophthalic acid ester may be prepared by adding isophthalic acid to an alcohol, adding a catalyst thereto, and reacting the resulting mixture in a nitrogen atmosphere; a step of removing the unreacted alcohol and neutralizing the unreacted acid; and a step of dehydrating and filtering by vacuum distillation.
The alcohol used in the pot method or blend method preparation method is examples, and may be an aliphatic or aromatic compound having an alkyl group with 1 to 20 carbon atoms, and specific examples thereof include at least kinds selected from methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol, pentanol and its isomeric alcohols, hexanol and its isomeric alcohols, heptanol and its isomeric alcohols, octanol and its isomeric alcohols such as 2-ethylhexanol, n-octanol, nonanol and its isomeric alcohols such as isononanol, 2-propylheptanol, 4-methyl-2-propylhexanol, 5-methyl-2-hexanol, decanol and its isomeric alcohols such as n-decanol, deca and its isomeric alcohols, aliphatic alcohols having an alkyl group with 1 to 20 carbon atoms such as dodecanol and its isomeric alcohols, and aromatic alcohols having an alkyl group with 1 to 20 carbon atoms such as phenol and benzyl alcohol.
As another example, the alcohol may be a branched fatty alcohol containing an alkyl group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon atoms, 8 to 9 carbon atoms, or 8 carbon atoms.
The alcohol used in the pan process may be used in a range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol%, based on 100 mol% of the mixture of terephthalic acid and isophthalic acid.
The alcohol used in the preparation method by the blending method may be used in a range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol%, based on 100 mol% of terephthalic acid.
The alcohol used in the preparation method of the blending method may be used in a range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol%, based on 100 mol% of isophthalic acid.
the catalyst used in the pot process or blend process is examples, which include at least examples of metal salts selected from sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, ethylbenzene sulfonic acid, propylbenzene sulfonic acid, butylbenzene sulfonic acid, alkylbenzene sulfonic acid, aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride, aluminum phosphate, etc., metal oxides such as heteropoly acids, natural/synthetic zeolites, cation and anion exchange resins, tetraalkyl titanates and their polymers, and specific examples of the catalyst include tetraalkyl titanates.
The amount of the catalyst to be used may vary depending on the kind, and is exemplified, and in the case of a homogeneous catalyst, it may be used in the range of 0.01 to 5 wt%, 0.01 to 3 wt%, 1 to 5 wt%, or 2 to 4 wt% with respect to 100 wt% of the total amount of the reactants, while in the case of a heterogeneous catalyst, it may be used in the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total amount of the reactants.
In this case, the reaction temperature may be in the range of 180 to 280 ℃, 200 to 250 ℃, or 210 to 230 ℃.
The plasticizer prepared as described above is contained in an amount of 5 to 150 parts by weight, 40 to 100 parts by weight, or 40 to 50 parts by weight per 100 parts by weight of a resin selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer, and thus a resin composition effective in both a composite formulation and a sheet formulation can be provided.
Exemplifying , the composition may be suitable for use in the manufacture of electrical wires, flooring materials, automotive interior materials, films, sheets, wallpaper or pipes.
The present invention will be specifically described below with reference to examples. However, the following examples are only illustrative of the present invention and do not limit the present invention.
< preparation example 1: Pot preparation 1>
1.5mol of terephthalic acid, 1.5mol of isophthalic acid and 9.0mol of 2-ethylhexanol were mixed in a 5-neck round-bottom flask equipped with a temperature sensor, a mechanical stirrer, a condenser, a Decanter (Decanter) and a nitrogen gas injection device, and 1.8g of tetraisopropyl titanate was added to the mixed reaction product as a reaction catalyst, and the temperature was raised to 220 ℃ to carry out the reaction for 5 hours.
After the reaction, the excess alcohol was extracted under reduced pressure, and subjected to a neutralization washing process using soda ash and distilled water, and dehydrated and filtered under reduced pressure distillation.
As a result of analyzing the obtained composition using a GC-Mass analyzer, it was confirmed that the composition consisted of compounds having the structures of the following chemical formulas 1 and 2 and the weight ratio was 50: 50.
[ chemical formula 1]
Figure BDA0002251534770000091
[ chemical formula 2]
Figure BDA0002251534770000092
< preparation example 2: Pot preparation 2>
In the above production example 1, the same procedure was repeated except that a mixed reactant in which 2.1mol of terephthalic acid, 0.9mol of isophthalic acid and 9.0mol of 2-ethylhexanol were mixed was used.
As a result of analyzing the obtained plasticizer using a GC-Mass analyzer, it was confirmed that the compounds having the structures of the above chemical formulas 2 and 1 shown in example 1 were composed at a weight ratio of 70:30 (chemical formula 2: chemical formula 1), respectively.
< preparation example 3: Pot preparation 3>
In the production example 1, the same procedure was repeated except that terephthalic acid was not used and a mixed reactant in which 3.0mol of isophthalic acid and 9.0mol of 2-ethylhexanol were mixed was used.
As a result of analyzing the obtained plasticizer using a GC-Mass analyzer, it was confirmed that the compound having the structure of the chemical formula 1 shown in example 1 was obtained.
< preparation example 4: preparation by blending method 1>
In the production example 1, the same procedure was repeated except that isophthalic acid was not used and a mixed reactant in which 3.0mol of terephthalic acid and 9.0mol of 2-ethylhexanol were mixed was used.
As a result of analyzing the obtained plasticizer using a GC-Mass analyzer, it was confirmed that the compound having the structure of the chemical formula 2 shown in example 1 was obtained.
The obtained compound was mixed with the compound obtained in preparation example 3 in a weight ratio of 70:30 (chemical formula 2: chemical formula 1).
< preparation example 5: preparation by blending method 2>
The compound obtained in preparation example 4 and the compound obtained in preparation example 3 were mixed in a weight ratio of 50: 50.
< Complex formulation >
The plasticizers obtained in preparation examples 1 to 5 were used as test pieces for experiments in examples 1 to 4 and comparative example 3, respectively.
The following products were prepared as test pieces for experiments of comparative examples 1 and 2, respectively.
DOP: LGflex DOP product name of LG chemistry
DOTP: product name of LG (strain) chemical GL300
Examples 1 to 4 and comparative example 3 using the plasticizers obtained in the above preparation examples 1 to 5, and test pieces using the commercially available plasticizers of comparative examples 1 to 2 were prepared by charging 100 parts by weight of PVC, 50 parts by weight of the plasticizer, 40 parts by weight of the filler, 5 parts by weight of the stabilizer, and 0.3 part by weight of stearic acid into a 3L high speed mixer (super mixer) according to ASTM D638, mixing at 100 ℃, 500rpm for 2 minutes, mixing at 1300rpm for about 10 minutes, then performing a roll grinding operation at 170 ℃ for 4 minutes to prepare 5mm sheets, and then performing a sheeting operation to preheat at 185 ℃ for 3 minutes, heat for 3 minutes, and cool for 3 minutes to prepare 1 to 3mm sheets, and prepare a plurality of "C" type (type "C") dumbbell test pieces.
The following physical property tests were carried out using the respective test pieces, and the results thereof are shown in table 1 below.
< test items >
QUV oven temperature 100 deg.C, ultraviolet irradiation for 200 hours, and then the test piece was taken out and △ E was confirmed by the presence or absence of bleeding and color difference meter.
Hardness (astm d 785):
after the hardness tester ("C" type) probe was completely dropped, the hardness values shown after 10 seconds were read. The hardness was obtained by performing tests at 3 points of each test piece and calculating the average value.
Tensile Strength, elongation [ ASTM D638]：
Elongation and tensile strength at the specimen break location were measured after pulling at crosshead speed (cross head speed)200mm/min using a test instrument u.t.m. The tensile strength (kgf/cm2) was calculated by load (load) (kgf)/thickness (cm) x width (cm), and the elongation (%) was calculated by elongation length (estion)/initial length x 100.
TABLE 1
As can be seen from the above Table 1, according to examples 1 to 4, the level equal to or higher than that of comparative example 1 was exhibited, and when compared with the DOTP product of comparative example 2, the improvement was exhibited in all of the items of bleeding phenomenon and light resistance, tensile strength, and the like.
The tensile strength was increased by 5% or more in examples 1 to 4 in which isophthalate and terephthalate were combined, as compared with comparative example 3 in which isophthalate was used alone.
It was also confirmed that the ester plasticizers of examples 1 to 4 each had an ether content of less than 1,000ppm as measured by gas chromatography (Agilent 7890GC, column: HP-5, carrier gas: helium) available from Agilent.
< sheet formulation >
Production of test pieces using the plasticizers obtained in the above-mentioned production examples 1 to 5 and the commercially available plasticizers of comparative examples 1 to 2, 100 parts by weight of PVC, 80 parts by weight of plasticizer, 2 parts by weight of secondary plasticizer ESO and 2 parts by weight of barium-zinc stabilizer were put into a 3L high speed mixer (super mixer) according to ASTM D638, mixed at 100 ℃ and 500rpm for 2 minutes, mixed at 1300rpm for about 10 minutes, and then subjected to roll grinding at 160 ℃ for 3 minutes to produce 5mm sheets.
The sheet was preheated at 185 ℃ for 3 minutes, heated for 3 minutes, and cooled for 3 minutes to prepare 1 to 3mm sheets, and a plurality of "C" type (type "C") dumbbell test pieces were prepared.
The following physical property tests were carried out using the respective test pieces, and the results thereof are shown in the following table 2.
< test items >
Hardness (ASTM D785), tensile strength, elongation [ ASTM D638]
The measurement was performed in the same manner as the above-described method.
Migration loss:
the initial weight (Wi) of each test piece was measured to the nearest 4 decimal places. After a sheet (3cmx3cm) was placed between polystyrene plates in an oven at 80 ℃ and a load of 1kg was applied for 72 hours, the test piece was taken out and stored in an incubator for 4 hours or more, and then the weight (Wq) of the test piece was measured, and the amount of migration was calculated by the formula (Wi-Wq)/Wi x 100.
Heating and weight reduction:
the initial weight (Wi) of each test piece was measured to the nearest 4 decimal places. The test piece was fixed by a clamp in an oven at 80 ℃ for 72 hours, taken out, stored in an incubator for 4 hours or more, and then the weight (Wo) of the test piece was measured, and the heating loss was calculated by the formula (Wi-Wo)/Wi x 100.
TABLE 2
Figure BDA0002251534770000131
As can be seen from table 2, in examples 1 to 4, the physical properties were improved by the same level or more as compared with comparative examples 1 and 2.
In particular, it was confirmed that the heating loss was about 1.4 to 1.5% in examples 1 to 4, while the heating loss was rapidly increased to 4.6% in comparative example 1. The rapid increase in the heating loss as in comparative example 1 means that the amount of the ester plasticizer present in the test piece is reduced by that amount.
The tensile strength was improved by 5% or more in examples 1 to 4 in which isophthalate and terephthalate were combined, compared with comparative example 3 in which isophthalate was used alone.
In examples 1 to 4 of the present invention, the transfer loss was reduced by about 3% as compared with comparative example 1, and the heating loss was reduced by 200% or more as compared with comparative example 1.
< measurement of physical Properties based on the number of carbon atoms >
In order to compare the difference in physical properties due to the number of carbon atoms in the terminal groups of isophthalate and terephthalate, the physical properties were measured under different conditions as shown in table 3 below. At this time, in the plasticizer, the contents of isophthalate and terephthalate were used at a 60:40 weight ratio, and a sheet was prepared by the same method as the preparation method of the sheet. The isophthalate and terephthalate esters in examples 5 to 10 were dialkyl isophthalate and dialkyl terephthalate, respectively.
TABLE 3
Figure BDA0002251534770000141
IP: esters of isophthalic acid
P: phthalic acid esters
TP: terephthalic acid esters
As is clear from Table 3, in examples 5 to 10 of the present invention, stable physical properties were ensured. In particular, in the case of examples 5 to 7 in which the terminal groups of isophthalate and terephthalate had 8 to 10 carbon atoms, the migration loss and the weight loss upon heating were significantly reduced by 10 times or more as compared with those of examples 8 to 10 in which esters having 7 or less carbon atoms were used.
In addition, in the case of mixing the isophthalate and the terephthalate, the heating loss was improved by about 3 times or more and the migration loss was also reduced by 9 times or more, as compared with comparative example 4 in which the terephthalate and the phthalate were mixed.
Therefore, the plasticizer of the present invention containing isophthalate and terephthalate is remarkably improved in migration loss and heating loss as compared with a plasticizer in which terephthalate and DOP are mixed, and is also more effective in environmental protection.
It is also found that the plasticizer of the present invention containing isophthalate and terephthalate, particularly when the number of carbon atoms in the ester terminal group is 8 to 10, has significantly improved physical properties as compared with the case where the number of carbon atoms is less than 8.
< measurement of physical Properties based on the mixing ratio of isophthalate and terephthalate >
In order to compare physical properties corresponding to the mixing ratio of isophthalate and terephthalate, the physical properties were measured by determining the contents of isophthalate and terephthalate at weight ratios of 90:10, 80:20, 70:30, 60:40, 40:60 and 0:100 and preparing a sheet by the same method as the preparation method of the sheet. The results are shown in table 4 below.
TABLE 4
Figure BDA0002251534770000151
As can be seen from Table 4, when the contents of isophthalate and terephthalate were 90:10, 80:20, 70:30, 60:40 and 40:60 by weight as shown in inventive examples 11 to 15, the hardness was significantly improved as compared with comparative example 5 in which terephthalate was used alone.
Furthermore, the hardness is also affected by the mixing ratio of isophthalate and terephthalate. That is, in the case of examples 11 to 14 in which the content of isophthalate was higher than that of terephthalate, the hardness was significantly reduced as compared with examples 15 and comparative example 5 in which the content of terephthalate was higher. The reduction in hardness is advantageous for improving the production efficiency of the product, and shows an improvement effect of the plasticization efficiency by excellent workability.
In examples 11 to 15, the migration loss and the heating loss were equivalent to those of comparative example 5, and the elongation was increased.
Therefore, as described in the present invention, the plasticizer of the present invention containing isophthalate and terephthalate has the same level of migration loss and heating loss, while the hardness and elongation are increased, thereby improving the productivity and processability of the product.

Claims (7)

  1. A process for preparing a plasticizer of , comprising the steps of:
    simultaneously charging isophthalic acid and terephthalic acid in a weight ratio of 50:50 to 70:30 in the presence of an alcohol, thereby obtaining a mixture;
    adding a catalyst to the mixture and reacting the mixture under a nitrogen atmosphere;
    removing unreacted alcohol and neutralizing the unreacted acid; and
    obtaining the plasticizer through reduced pressure distillation dehydration and filtration,
    wherein the plasticizer is an ether-free plasticizer in which the content of an ether component contained in the plasticizer is 1,000ppm or less,
    wherein the weight ratio of isophthalate to terephthalate in the plasticizer is 50:50 to 70: 30.
  2. 2. The method of claim 1, wherein the alcohol is 2-ethylhexanol.
  3. 3. The method of claim 1, wherein the isophthalate has the structure of formula 1 and the terephthalate has the structure of formula 2:
    [ chemical formula 1]
    Figure FDA0002251534760000011
    [ chemical formula 2]
    Figure FDA0002251534760000012
  4. 4. The process of claim 1, wherein the catalyst is a tetraalkyl titanate.
  5. 5. The process of claim 1, wherein the catalyst is used in an amount ranging from 0.01 wt% to 5 wt%, based on 100 wt% of the total amount of reactants.
  6. 6. The process of claim 1 wherein the alcohol is used in a molar percentage of 150 to 500 percent, based on 100 percent molar percentage of isophthalic acid.
  7. 7, A method of making a plasticizer comprising the steps of:
    preparing an ester mixture containing terephthalate and isophthalate; and
    mixing the terephthalate and isophthalate in a weight ratio of isophthalate to terephthalate of 50:50 to 70:30 to obtain a plasticizer, and
    wherein the plasticizer is an ether-free plasticizer, and the ether-free plasticizer is a plasticizer in which the content of an ether component contained in the plasticizer is 1,000ppm or less.
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